Title of Invention


Abstract The present invention provides a very narrow band pulse excimer laser capable of producing pulses at a rate in the range of about 500 to 2000 Hz with enhanced energy dose control and repoducibility. Very small quantities of a stabilizing additive consisting of oxygen or a heavy noble gas (xenon or radon for KrF lasers, or krypton, xenon or radon for ArF lasers), are added to the gas mixture. Tests performed show substantial improvements in energy stability with the addition of about 30 ppm of xenon to a KrF laser. Tests show improved performance for the ArF Lasers with the addition of about 6-10 ppm of Xe or 40 ppm of Kr. In a preferred embodiment, very narrow bandwidth is achieved on a KrF laser by reducing fluorine partial pressure to less than 0.10 percent and by increasing the reflectance of the output coupler to greater than 25 percent. In a preferred embodiment, prior art fused silica beam expansion prisms used in the prior art line narrowing module were replaced with calcium fluoride prisms (see fig - specification devoid of reference numeros).
Full Text This is a Continuation-In-Part Application of Serial No. 08/947,474, Very Narrow Band KrF Laser, filed October 10, 1997 and Serial No. 09/082,139, Narrow Band Excimer Laser with Gas Additive, filed May 20, 1998. This invention relates to lasers and in particular to narrow band lasers.
Excimer lasers are currently becoming the workhorse light source for the integrated circuit lithography industry. A typical prior art KrF excimer laser is depicted in FIG. 1 and FIG. 9. A pulse power module 2 provides electrical pulses lasting about 100 ns to electrodes 6 located in a discharge chamber 8. The electrodes are about 28 inches long and are spaced apart about 3/5 inch. Typical lithography lasers operated at a high pulse rate of about 1,000 Hz to 4,000 Hz. For this reason it is necessary to circulate a laser gas (about 0.1 percent fluorine, 1.3 percent krypton and the rest neon which functions as a buffer gas) through the space between the electrodes. This is done with tangential blower 10 located in the laser discharge chamber. The laser gasses are cooled with a heat exchanger also located in the chamber. Commercial excimer laser systems are typically comprised of several modules that may be replaced quickly without disturbing the rest of the system. Principal modules are shown in FIG. 1 and include:
Laser Chamber 8,
Pulse Power Module 2, consisting of three submodules
Output coupler 16,
Line Narrowing Module 18
Wavemeter 20

Computer Control Unit 22 Peripheral Support Sub systems Blower 10
The discharge chamber is operated at a pressure of about three atmospheres. These lasers operate in a pulse mode at about 600 Hz to about 1,000 Hz, the energy per pulse being about 10 mJ and the duration of die laser pulses is about 15 ns. Thus, the average power of the laser beam is about 6 to 10 Watts and the average power of the pulses is in the range of about 700 KW. A typical mode of operation is referred to as the "burst mode" of operation. In this mode, the laser produces "bursts" of about 50 to 150 pulses at the rate of 1,000 pulses per second. Thus, the duration of the burst is about 50 to 150 milliseconds. Prior art lithograph, excimer lasers are equipped with a feedback voltage control circuit which measures output pulse energy and automatically adjusts the discharge voltage to maintain a desired (usually constant) output pulse energy. It is very important that the output pulse energy be accurately controlled to the desired level.
It is well known that at wavelengths below 300 nm there is only one suitable optical material generally available for building the stepper lens used for chip lithography. This material is fused silica. An all fused silica stepper lens will have no chromatic correction capability. The KrF excimer laser has a nautical bandwidth of approximately 300 pm (full width half maximum). For a refractive system (with NA > 0.5) - either a stepper or a scanner - this bandwidth has to be reduced to below 1 pm. Current prior art commercially available laser systems can provide KrF laser beams at a nominal wavelength of about 248 nm with a bandwidth of about 0.8 pm (0.0008 nm). Wavelength stability on the best commercial lasers is about 0.25 pm. With these parameters stepper makers can provide stepper equipment to provide integrated circuit resolutions of about 0.3 microns. To improve resolution a narrower

bandwidth is required. For example, a reduction of a bandwidth to below 0.6pm would permit improvement of the resolution to below 0.25 microns.
Argon fluoride, ArF excimer lasers which operate at a wavelength of about 193 nm
using a gas mixture of about 0.08 to 0.12% fluorine, 3.5% argon and the rest neon,
5 are beginning to be used for integrated circuit lithography. F2 lasers produce laser
radiation at wavelengths of about 159 nm. The gas mixture typically is 0.1 % percent fluorine and the rest helium or neon.
Gas discharge laser typically use a preionizer technique for preionizing the gas between the electrodes prior to the main electrical discharge. Examples of these
10 preionizers are spark gap preionizers and corono discharge preionizers. Spark gaps
produce ions with a discharge between two electrodes like an automatic spark plug. A corono discharge preionizer produce ions by creating a corono of ions adjacent to a conductor at high voltage. A typical corono discharge preionizer is described in U.S. Patent No .5,337,330 which is incorporated herein by reference. The ionization
15 produced by these preionizers produces ultraviolet radiation which in turn reacts with
the laser gas to generate a substantial ion population in the laser gas between the electrodes. Typically spark gap preionizers produces higher energy ultraviolet radiation than corono discharge preionizers, but the radiation from the corono discharge preionizers lends to be much more uniform.
20 It is known that the addition of about 10 to 50 ppm of oxygen to an excimer laser gas
mixture can be used to stabilize the efficiency and performance of the laser. These additives improve the preionization efficiency of the laser. See, for example, U.S. Patent No. 5,307,364. Small quantities of xenon have been proposed as a gas additive for COj lasers. See Japan Patent Number JP 60180185 issued in 1984 based
25 on a patent application filed on February 27, 1984. In a 1995 article entitled,

Tranmission Properties of Spark Preionization Radiation in Rare-Gas Halide Laser
Gas Mixes, (IEEE Journal of Quantum Electronics, Vol. 31, No. 12, December 1995),
the author discusses gas additives to enhance preionization of rare-gas halide lasers.
This paper deals with lasers utilizing spark gap preionization. Spark gap
5 preionization is known to produce high energy photons which in turn preionizes laser
gas between the laser electrodes. The author points out that the ionization potential
of xenon is too high (i.e., greater than the preferred ionization potential of s 10 ev);
however, the author suggests that it might be possible to use small quantities of xenon
in lasers which have transmission windows at vacuum ultraviolet wavelengths 10 nm or photon energies in excess the 12.1 ionization potential of xenon. The article
infers that spark gap photons have energies less than 10 ev and suggests that higher energy photons such as x-rays could be used to excite xenon if used as an additive.
The actual performance of integrated circuit lithography equipment then depends
critically on maintaining minimum bandwidth of the laser throughout its operational
15 lifetime, and also minimizing the laser"s energy variation from pulse-to-pulse.
Therefore, a need exists for a reliable, production quality excimer laser system, capable of long-term factory operation and having accurately controlled pulse energy stability, wavelength, and a bandwidth.
20 The present invention provides a very narrow band pulse gas discharge laser capable
of producing pulses at a rate in the range of about 500 to 4000 Hz with enhanced energy dose control and reproducibility. Very small quantities of a stablizing additive consisting of oxygen or a heavy noble gas (xenon or radon for KrF lasers, or krypton, xenon or radon for ArF lasers or Fj lasers), are added to the gas mixture.
25 Tests performed show substantial improvements in energy stability with the addition


wo oi/oe^«- "Pei¥«s«M«i4i
of about 30 ppm of xenon to a KrF laser. Tests show improved performance for the ArF lasers with the addition of about 6-10 ppm of Xe, 40 ppm of Kr or about 3 to 10 ppm oxygen. In a preferred embodiment very narrow bandwidth is achieved on a KrF laser by reducing fluorine partial pressure to less than 0.10 percent and by increasing the reflectance of the output coupler to greater than 25 percent. When operating in a burst mode performance of the laser is improved by pre-pulsing the laser; i.e., providing a few pulses prior to the start of the burst. In a preferred embodiment, prior art fused silica beam expansion prisms used in the prior art line-narrowing module were replaced with calcium fluoride prisms.


FIG. 1 is a drawing showing the principal elements of a prior art commerical KrF excimer laser used for integrated circuit lithography.
FIG. 2 is a simplified electrical drawing of a solid state pulse power circuit.

15 / FIG. 3 are graphs comparing the results of a solid state pulse power circuit to a prior
art thyratron based circuit.
FIG. 4 is a graph of operating voltage during a pulse.

FIG. 5 shows a typical variation of operating voltage and bandwidth over an 800 million pulse period.
FIG. 6 is a simplified sketch of a KrF laser system.
FIG. 7 is a sketch of the principal element of a line-narrowing module.
5 FIGS. 8A-8J show results of an additive of Xe to a :KrF laser..
FIG. 9 is a drawing of a prior art commercial KrF lithography laser.
FIG. 10 shows the relationship between fluorine, operating voltage and pulse energy.
FIG. 11 shows the variation of line width with fluorine concentrations.
FIGS. 12A and 12B show pulse shape with different fluorine concentrations.
10 FIG. 13 is a chart of average pulse energy during the first 125 pulses during burst
mode operation with no oxygen in the chamber where data firom 50 bursts were averaged.
FIG. 14 is a chart similar to FIG. 13 showing average pulse energy with oxygen at 0 ppm, 25 ppm and 49 ppm.
15 FIG. 15 is a chart showing 3-sigma statistics of the data plotted in FIG. 14.
FIG. 16 shows the effect of repetition rate udth two gas additive.


wo 01/QS228 RCT/I1S00/1S141
FIGS. 17A and B compares the effects of oxygen and xenon.
FIG. 18 shows the effect of having a cold trap in the gas path.
FIGS. 19A and B compares the effects of 1, 2 and 10 pre-pulses vAth no pre-pulses.
FIG. 20 summarizes some prepulsing data.
Preferred embodiments of the present invention are described below.
FIG. 1 shows the principal elements of a commercial excimer laser system of the type used today in integrated circuit lithography.
10 The Chamber
The discharge chamber 8 is a vessel, designed to hold several atmospheres of
corrosive gases. These vessels are designed to known safety standards, such as those
specified by ASME. The two electrodes separated by a gap of 1.2 to 2.5 cm define
the discharge region. The cathode is supported by an insulating structtire since it is
15 connected to the high voltage, while the anode is attached to the metal chamber as it
is at ground potential. Preionization is done by corona discharge preionizers located on either side of the discharge region. Due to the corrosive nature of the gas the chambers use particular metals chosen to resist fluorine attack. The fluorine gas

however, still reacts with the chamber internal parts such as chamber walls and electrodes; thus consuming fluorine and generating metal fluoride contaminants.
Since the laser is pulsed (500 to 4000Hz), it is essential to clear the discharge region between pulses - a task preferably performed by a tangential blower, which is
5 magnetically coupled to an external drive source. Heat is extracted from the laser gas
by means of a water-cooled finned heat exchanger inside the chamber. Metal fluoride dust is trapped by means of an electrostatic precipitator not shown. A small amount of laser gas is extracted from the chamber and is passed over negatively charged high field wires to trap the dust. The dust-free gas is then released over the windows to
10 keep them clean. The gas is driven through the precipitator by the differential
pressure built up inside the laser chamber due to the high velocity flow.
Pulse Power Module
This preferred embodiment utilizes a solid state pulsed power module (SSPPM) circuit shown in FIG. 2. The 20KV power supply of prior art thyratron systems is
15 replaced by a IkV supply. The thyratron switch is replaced by an SCR switch that
does not feed Cp directly, but instead switches the energy of CQ into a pulse compression circuit formed by Cj, Cj, C3, a step-up transformer, and three saturable inductors. The operation of this circuit is as follows. The DC charge stored on CQ is switched through the SCR and the inductor LQ into Cj. The saturable inductor, L\,
20 holds off the voltage on C\ for approximately 2.5 ns and then becomes conducting,
allowing the transfer of charge from Cjto C2- The second saturable inductor, L2, holds off the voltage on C2 for approximately 500ns and then allows the charge on C2 to flow through the primary of 1 -.20 step-up transformer. The output from the step-up transformer is stored on C3 until the saturable inductor L3 becomes
25 conducting in approximately 100-150 ns. The charge is then finally transferred
through L3 into Cp and laser discharge occurs.

Spectral Narrowing
As stated earlier, bandwidth (FWHM) of a free running KrF excimer laser is
approximately 300 pm. Currently, excimer steppers utilize lasers spectrally narrowed
to between 0.8 and 3 pm, FWHM, depending on the NA of the lens. It should be
5 noted that the integrated energy spectrum and the spectral width at 95% energy are
more critical to stepper performance than the FWHM value. However, most users find it convenient to talk about FWHM instead of spectral width at 95% energy.
Spectral narrov^ng of a KrF laser is complicated by its short pulse duration (10 to 15 ns, FWHM) and UV wavelength. The short pulse results in very high intra-cavity
10 power (~ 1 MW/cm^), and the short wavelength can thermally distort optical
materials due to their high absorption co-efficient at 248 nm. Also, the total number of round trips through the resonator (which includes the line narrowing optical elements) for a typical laser is small, about 3 to 4. If the single pass linewidth through the resonator is denoted by )AX,, then the fmal linewidth )AAf after n passes is given
15 by:
AX, V"
Therefore, the single pass linewidth of the optical system should be, at most, a factor
of two higher than the final linewadth. In fact, time resolved spectral measurements
by Applicants fellow workers indicate that the spectral linewidth could decrease by
a factor of two from the start of the pulse to the tail of the pulse. Therefore, the
20 efficiency of converting the broadband spectrum to line narrowed spectrum (i.e. from
300 pm to -9-


WO01/O8a9«- BCT/US00/18K1
The common technique of ILne-narrov^ing the KrF laser is by introducing wavelength
dispersive optical elements in the resonator. Three types of dispersive elements can
be used: prisms, etalons and gratings. The use of a high dispersive grating in a
Littrow configuration is the simplest and most effective spectral line narrowing
5 technique. Because the grating is a dispersive element, the line-wddth is proportional
to the beam divergence. To get narrow line-width, a small beam divergence is
required. Hence in a preferred design, 2 slits and a 3 prism-beam expander is inserted
in the laser resonator. The principal elements of a preferred line-narrowing module
are shown in FIG. 7. These include 3 prisms; 30, 32 and 34, a tuning mirror, 3C and
10 an eschelle grating, 38. The mirror is pivoted to change the wavelength of the laser.
Improved Spectral Performance
Applicants and their fellow workers have designed, built and tested laser KrF excimer laser equipment capable of meeting linewidth specifications of 0.50 pm at FWHM with 95% of the energy of the laser beam within 2 pm. These results have been
15 demonstrated on new, raid-age and old discharge chambers for 80 million pulses
proving that the system is capable of continuous performance within these specifications over the normal life of the equipment with usual maintenance. These results represent an approximately 50 % improvement over the prior art narrow band excimer laser technology.
In order to achieve this improved performance Applicants have improved both the laser equipment and the operating parameters of the laser.
Reduction of Fluorine Consumption
In preferred embodiments of the present invention which have been built and tested
25 by Applicants, great care was taken to eliminate materials from the discharge


WOOli^WS BCT/US00/1&144
chamber that consume fluorine. Fluorine consumption in a discharge chamber is due
to fluorine reaction with materials in the chamber. These reactions typically produce
contaminants, which result in deterioration of laser performance. In order to
minimize fluorine consumption, this preferred embodiment include the following
5 specific features:
The chamber walls are aluminum coated with nickel.
The electrodes are brass.
All metal 0-rings are used as seals.
Insulators are all ceramic and fluorine compatible.
10 Alumina is applicants preferred insulator material.
An electrostatic filter is provided as in prior art designs to filter
contaminants produced during operation.
The fan unit is driven using a magnetically coupled motor located outside
the sealed discharge chamber using a prior art technique.
15 During manufacture, parts are precision cleaned to remove potential
contaminants. After assembly, the chamber is passivated with fluorine.
Reduction of Nominal Fluorine Concentration
20 This preferred embodiment requires substantial changes.in operating procedures and
parameters of the laser system in order to achieve the desired very narrowband output. The fluorine concentration in reduced fi-om 0.1% (30 kPa) to about 0.06% (18 kPa). The total gas pressure is about 300 kPa. (The Kr concentration is maintained at the prior art level of about 1.3% and the remainder of the laser gas is
25 neon.) During operation, fluorine will be gradually depleted. Constant pulse energy
is obtained by gradually increasing the laser operating voltage in accordance with

WO Ol/OSSfe- .PCT/LTSOO/18141
prior art techniques. Injections of a mixture of fluorine and neon are made
periodically (typically at intervals of about 1 to 4 hours) to make up for the depletion
of fluorine in accordance with techniques well known in the excimer laser prior art.
During this procedure, the fluorine concentration is preferably maintained within the
5 range ofbetween about 0.055% and 0.065% and the operating voltage is maintained
within a corresponding range appropriate to maintain constant pulse energy. For example, in a preferred embodiment this range was 670 Volts to 790 Volts.
Increase in Reflectivity of Output Coupler
In this preferred embodiment of the present invention the reflectivity of the output
10 coupler has been increased from about 10% which was typical of prior art narrow
band excimer lasers to about 30%. This was done to help make up for the loss of laser efficiency resulting from the reduced fluorine concentration.
Switch to Calcium Fluoride Prisms
The change in the reflectivity of the output coupler from 10% to 30% had the effect
15 of approximately doubling the light passing through the line-narrowing module. The
additional heat generated by this additional illumination in the prior art fused silica
prisms caused thermal distortion in the prisms. To solve this problem the fused silica
prisms were replaced with calcium fluoride prisms. Calcium fluoride has higher
thermal conductivity and could handle the additional energy without imacceptable
20 distortion.

wo 01/0^»fr PCT/USO0/18H1
Fluorine Reduction
FIG. 10 describes the relationship between operating voltage, fluorine concentration and pulse energy. This graph shows that as the fluorine concentration decreases the voltage must be increased to maintain the desired output of 10 mJ per pulse.
5 However, in this particular embodiment the upper limit on the operating voltage is
800 Volts. Note that vAlh a 10% R output coupler the lowest fluorine concentration corresponding to an output of 10 mJ would be 25 kPa at which point the operating voltage would have risen to 800 Volts. However with a 30 % R output coupler, the fluorine concentration could be reduced to as low as about 20 kPa while still
10 maintaining a 10 mJ pulse energy with the operating voltage at slightly under 800
Volts. FIG. 11 shows actual test results of reducing the fluorine concentration on line width (measured at FWHM and at 95 % pulse energy) for both continuous pulses at 1000 Hz and for 500 pulse bursts and 1 OOOHz. For this particular test the output coupler had a 25 % reflectivity. Typical laser pulse shapes for prior art KrF systems
15 and these very narrowband KrF lasers are compared in FIGS. 12A and 12B. Note
that with the very narrowband lasers, energy is shifted to the latter part of the pulse, vv"hich represents photons, which have had the benefit of more trips through the line-narrowing module. As a result, the integrated pulse spectral linewidth of the laser is reduced.
As indicated in the Background section of this specification, a typical mode of
operation of a KrF laser is a "burst mode" in which bursts of about 125 pulses are
produced at the rate of 1000 pulses per second. The burst lasts for about 125
milliseconds and there typically is a "dead time" of a fraction of a second between
25 bursts. Applicants" KrF laser contains about 0.017 cubic meters of laser gas and the
flow rate of gas between the electrodes produced by blower 10 is about 0.228 cubic

meters per second. This would imply a total gas circulation time of about 75 milliseconds; however, flow in the chamber is far from uniform and portions of the gas circulates much quicker. The speed of the gas between the electrodes is about 20 meters per second and the Applicants estimate that the fastest gas makes the trip in
5 about 20 miUiseconds. Applicants have discovered a "slug effect" generated by the
first or the first few pulses in a burst. This slug effect is shown in FIG. 13 that is a plot of pulse energy for each of the 123 pulses of a typical burst of 123 pulses averaged over 50 bursts. There is a large drop-off after the first pulse and another large dip after the 21st pulse, i.e. about 21 milliseconds following the first pulse.
10 This dip is extremely reproducible and the timing of the dip is in proportion to the fan
speed. Applicants do not know the exact cause of this first 40 milliseconds of very reproducible erratic performance but have identified it as the "slug effect" and believe it is attributable to chemical efifects generated when "clean" laser gas passing between the electrodes is blasted with 16,000 to 20,000 volts during the first pulse or the first
15 few pulses. The gas passing between the electrodes during the first 20 milliseconds
is substantially all "clean" laser gas but after about 20 milliseconds, gas electrocuted during the first pulse begins to pass back between the electrodes. After about 39 milliseconds into the burst, the gas in the laser is thoroughly mixed and the slug effect disappears.
Applicants, through their experimentation have discovered that substantial
improvements in laser performance can be realized by the addition of very small
quantities of selected gases. Prior art teaches that about 10 to 50 ppm oxygen
improves energy stability. However, these quantities of oxygen produce a decrease
25 in the power output which tends to outweigh the improvements in stability.
Applicants have discovered that quantities of oxygen smaller than 10 ppm provide

wo 01/08*?fr PCT/USOO/18141
significantly improved stability without significant detrimental effects. Applicants have also discovered that the addition of very small quantities of heavy noble gases provides substantial improvements without significant detrimental effects.
Xenon Additive
5 The effect of xenon additives on operating voltage and efficiency are given in FIG.
8 A. The rate of laser efficiency decrease is about 0.15% per 1 ppm of xenon which is not good; but the energy stability was noticeably improved for all xenon concentrations and exhibited a slight maximum around 30 ppm. This maximum is not apparent from the drawing. All subsequent tests were performed with a xenon
10 concentration of 30 ppm.
The energy versus voltage characteristic is given in FIG. 8B. The energy is lower with xenon over the entire range.
The burst transients are compared in figures 8C and 8D. With xenon the energy transient is reduced, especially for the first ten pulses, which makes it easier on the
15 energy algorithm. A major improvement with xenon is found in the energy stability,
which is reduced, for all pulse numbers. This is in contrast to the effect of oxygen which only works on the reentrant. In fact, this chamber does not exhibit any reentrant, so the reentrant effect of xenon could not be confirmed with this chamber. For a blower speed of 4200 rpm the reentrant should occur at about 20 ms. (Note,
20 subsequent tests with chambers that do exhibit a reentrant effect confirm that 30 ppm
xenon does produce at least a small reduction in the reentrant effect.
The laser energy is almost independent of repetition rate (see FIG. 8E), with the xenon mixture giving consistently lower values. By contrast, the improvement in dose stability with xenon is most noticeable at higher pulse rates. At 1 kHz the

wooizesiw ^TTaisoo/isni
energy stability is probably dominated by effects unrelated to discharge stability such
as noise in the data acquisition and high voltage power supply regulation. We are
usmg two paralleled 5000 power supplies with >3V of dither. The dose stability in
a 2 kHz mode is displayed in FIG. 8F. Addition of 30 pm of xenon reduces the dose
5 enorby about 0.1%. This is a substantial improvement.
No effect of xenon on any other beam parameters (spatial profiles and divergence, linewidth) was observed. Occasionally, it appeared that xenon mixtures produce narrower linewidth. Howeyer, this was most likely an artifact produced by the fused silica beam expanding prisms. It takes more time to generate a xenon
10 mixture, which allows the prisms to cool down. Recorded linev^ddths were 0.65 pm
FWHM and 1.90 pm 95%. The linewddths would possibly be narrower with CaFj prisms because of better thermal properties. A comparison of the temporal profiles at 10 mJ of energy is displayed in FIG. 8G. The 30 ppm xenon mixture exhibits a typical waveform for higher charging voltages (667V 30 ppm Xe, 651V w/o Xe),
15 namely larger initial spike and shorter duration. From this, one would expect a larger
linewidth with xenon, which was not observed. Nevertheless, the differences are very small and only reflect one particular shot. Unfortunately, no averaged pulse profiles were recorded.
Explanation of Results of Xenon Tests
20 So why does xenon help at all and why in such small concentration? Some insight
is gained by observing the peaking capacitor voltage Vcp (FIG. 8H). For the same charging voltage Vco of 650V, gas breakdown occurs 2 ns earlier v/ith a xenon mixture. The obvious explanation is improved pre-ionization. Xenon can be ionized by light shorter than 93 nm whereas krypton and neon have thresholds of 85 nm and
25 58 nm, respectively (R.S. Taylor, IEEE JQE v. 31, p. 2195,1995). Therefore, xenon

WO01/0te?« J?CT/US00/18M1
can use a large part of the corona light that otherwise would just be transmitted. Even
at 30 ppm the xenon concentration is seven orders of magnitude larger than typical
pre-ionization electron densities. This means, the amount of xenon atoms is not a
limiting factor. The absorption cross section of xenon is 1500 cm"" which translates
5 into a 50% transmission after 5 cm for 30 ppm at 315 kPa. This would explain why
higher xenon concentrations are less efficient, the 90 nm light is already being filtered out very close to the PI tube.
There are other scenarios possible like faster current avalanching due to the lower
ionization potential of xenon. This, however, is hindered by the low concentration.
10 Another possibility is a change in the spectral content of the corona light, which may
have beneficial effects. In fact, the discharge containing xenon visually appears much brighter, primarily due to yellow components.
Better pre-ionization may also help the minimum clearing ratio (a measure of gas
flow between electrodes between pulses). There is a very slight improvement for
15 lower charging voltages (FIG. 81). At 650V (lOmJ) 3800 rpm is barely enough to
prevent down-stream-arcing and dose stability improves when going to 4200 rpm. At 800V arcing is much more severe, although largely aggravated by blips.
Xenon Effects Survives Refills
Very early in the experiments a strange phenomenon was encountered: the beneficial
20 effect of xenon survives refills. Due to this, detailed studies on the influence of the
exact xenon concentration became difficult, or at least time consuming. What is happening is that after the laser was operated with a xenon containing mixture and refilled without xenon, the energy stability would stay at a low level. Not as good as with xenon, but somewhere in between. A number of experiments were conducted

wo 01/0«Effi^ PCT/USOO/18141-
to help understand the mechanism of this memory effect. The difference in dose stability between a truly xenon-free mixture and a pre-conditioned mixture is only 0.05%. This difference is too small to allow any hard conclusions, so only some general trends can be outlined.
5 There are two possibilities; either xenon physically stays in the chamber or it altars
the chamber in a long lasting way. Such an alteration could be smoothing or cleaning of electrodes or windows. A first refill after a xenon fill was operated for four hours and 2 million shots without losing good stability. Four to five refills, however, with much fewer shots and in a shorter time completely bring the chamber back to normal.
10 This rather supports the theory that xenon stays in the chamber. The same conclusion
is drawn from the fact that simply filling with xenon and never firing the laser also helps subsequent fills.
Contrary to energy stability, the operating voltage is entirely independent of the previous history. This means that not a large percentage of the xenon can be carried
15 over to the next fill. There are different ways how xenon could remain in the laser.
Since xenon is a very heavy gas it may collect preferably on the bottom or in the MFT when the blower is not running. In that case, it should be removable by pumping the chamber to a pressure much lower than what is available with the membrane pump. This still did not prevent the memory effect. Which would suggest
20 that xenon gets trapped due to its large size in porous materials or virtual leaks in the
Extended Xenon Test
FIG. 81 presents an extended run in 2 kHz mode with a 30 ppm xenon mixture. No data are available without xenon, so this is merely a statement how well the chamber

can perform. The total pressure did not increase during the test. The linewidth
increases for the first 2 hours, typical of heating of the fused silica LNP. Thereafter,
the normal trend of decreasing linewidth for decreasing fluorine concentration is
observed. However, the linewidth continues to decrease and only stabilizes after 3
5 injects.
The voltage continues to increase and also only stabilizes after 3 injects. In conjunction with the linewidth data the voltage increase is most likely not due to any impurities but simply because the mixture gets leaned out. Once the voltage is increased the injection intervals shorten because the discharge is no longer blip-free.
10 During the test a fantastically low fluorine consumption rate was observed.
Immediately after the refill, the laser was running for an incredible 15 hours and 28 million pulses without injection.
In summary, this test shows that with an addition of a small amount of xenon to the
gas mixture a KrF chamber can operate within specifications for 95% linewidth and
15 dose stability. Very low fluorine consumption was observed.
Heavy Noble Gas Additives in ArF Laser
Applicants have conducted experiments with very small quantities of Kr and Xe
added to a typical ArF gas mixture. (A typical mixture is about 0.08 to 0.12%
fluorine, 3.5 % argon and the rest neon.) Both Kr and Xe substantially reduced the
20 average 3 sigma of the laser. Without the additives the 3 sigma for the laser was
about 5%. About 6-10 ppm of Xe reduced 3 sigma to about 4% (a 20% improvement). For the same improvement with Kr about 40 ppm were required.

As with the KrF laser the additives reduced the output of the laser. For the same
discharge voltage pulse energy was reduced by about 1 % for each ppm of Xe and
about 0.2% for each ppm of Kr. Thus, an 8 ppm of xenon the pulse energy would be
reduced by 8% and 40 pm of Kr would reduce the output by roughly the same amount
5 about 8%.
Very Small Ouantitv Oxygen Addition
FIGS. 14 and 15 show the effect on the slug effect in a KrF laser of adding minute
quantities of oxygen to the laser gas. FIG. 14 shows a dramatic reduction in the
energy decrease occurring at about 22 to 35 milliseconds into the burst. FIG. 15
10 shows that the 3-sigma variation is also dramatically reduced with the addition of
oxygen in the range of about 25 to 49 parts per million, but 25 ppm produces a reduction of about 10% in the pulse energy and 49 ppm produces a reduction of about 20% Applicants have determined about 5 ppm provides significant improvement in stability without significant detrimental effects.
15 Argon Fluoride Laser - Elimination of Gas Refill Syndrome v^th Oxvgen
Applicants have discovered that the addition of oxygen also improves performance
of very narrow band ArF lasers. Applicants have identified what they call a gas refill
syndrome. They have discovered that immediately after replacing the laser gas in an
ArF very narrow band laser, the laser performs very poorly in that the pulse energy
20 and laser energy is substantially reduced. However, after setting overnight, the next
morning the laser performs within specification.

This gas refill syndrome was eliminated with the addition of an extremely small quantity of oxygen such as about 2 to 3 parts per million. Thus, the preferred laser gas mixture for the very narrow band ArF excimer laser is:
3.5 percent argon
5 0.1 percent fluorine
2-3 parts per million oxygen remainder neon to 3 atmospheres.
Additional quantities of oxygen were added but the oxygen addition beyond 5ppm
had no significant beneficial effect. Recommended ranges of oxygen in both KrF and
10 Arf lasers is between about 2 to about 7 ppm. Recommended ranges of Xe for KrF
lasers is less than about 30 to 40 ppm. Recommended ranges of Kr for ArF lasers is less than about 40 ppm and recommended Xe ranges is less than about 10 ppm.
Additional Test Results
15 Further testing performed by Applicants have confirmed that small quantities of
oxygen, preferably less than 10 ppm and small quantities of xenon also less than about 10 ppm substantially ArF laser performance.
Extensive testing, however, has not confirmed which is the best additive. At very
low pulse repetition rates, the oxygen additive performs much better than xenon;
20 however, at repetition rates of in excess of 500 pulses per second, performance is
about the same. Applicants have determined that at high repetition rates of about 1000 pulses per second to about 3000 pulses per second, laser pulse energy is very slightly greater with the xenon than with oxygen of like quantities and with

wo oi/oaas- 9GiaisamuAequivalent other conditions. Tests have also shown in both cases pulse energy output decreases with increasing concentrations of either of the additives. Based on the 3000 pulses per second operation, Applicants conclude that the effect of Xe at higher repetition rates is more pronounced than with Oj.
5 Applicants" tests have shown that the poor performance with the xenon additive at
low pulse rates can be greatly minimized by maintaining cooling water flow through the chamber heat exchanger. This result causes Applicants to believe that the discharge creates a molecular species which is detrimental to laser performancew but that by maintaining a certain temperature of the chamber, about 60 to 75°C, this effect
10 can be reduced substantially.
FIGS. 16 through 18 show the results of these additional tests. FIG. 16 shows the
results of an ArF laser operating at 2 and 3 kHz pulse rate with 70°C gas temperature.
FIGS. 17A and B shows that the xenon additive provides slightly more stable
operation at high repetition rate than the oxygen additive. FIG. 18 demonstrates the
15 low repetition rate problem with the xenon additive and the effect of having a cold
sink in the gas path.
As described above in the section entitled "BURST MODE OPERATION" and
shown in FIGS. 13, 14 and 15, operation of the laser in a burst mode results of the
20 laser in a burst mode results in a slug effect which is related to the laser gas
circulation time. Applicants have determined that some of the adverse effects of the slug effect can be minimized by pre-pulsing the laser. This involves providing a few pulses prior to the start of each burst. In general only a few pre-pulses will produce even better performance.

wo 01/08^8 PCTAJSOO/lSlil
FIGS. 19A and B shows the effect on an ArF laser operating at a 2000 pulse per
second pulse rate pre-pxilses 10 ms prior to the start of bursts. The chart compares
no pre-pulses with 1,2 and 10 pre-pulses. The gas transmit time was about 20 ms.
FIG. 20 summarizes the test results of pre-pulses shown in FIG. 19. The chart
5 indicates that pre-pulses at 10 ms in advance of the pulse cuts the slug effect in half.
From this data Applicants recommend about 1 to 10 pre-pulses 20 ms prior to the burst and at 10 ms prior to the burst as an alternative. JTiese pre-pulses will produce a slight improvement in energy stability during burst mode operation.
Similar beneficial effects on energy stability wdth pre-pulsing in KrF lasers has also
10 been observed by the Applicants.
Although this very narrow band laser has been described v^rith reference to particular embodiments, it is to be appreciated that various adaptations and modifications may be made to the invention. Although Applicants did not test radon in its lasers, they
15 have concluded that very small quantities of radon gas would improve energy
stability without substantial negative effects. Radon should be easier to ionize than any other noble gas and it will not form long-lived compounds with fluorine. Therefore, it should like xenon in the KrF laser and krypton in the ArF and KrF lasers aid preiotuzation. Applicants expect that the best concentration for radon would be
20 similar to those discussed above for Xe and Kr. For example, soxu-ces of oxygen can
be pure oxygen or any of the oxygen referred to in U.S. Patent 5,307,364. Also, the source of oxygen could be a solid such as aluminum oxide or potassium, which could be contained within the chamber environment and the oxygen emission, could be controlled with temperature. The performance of FT lasers should also be improved
25 by additives of the types and quantities described above. The Fj laser is substantially

similar to the KrF and ArF lasers described above except the preferable laser gas is a mixture of about 0.1% Fj and the rest helium. An Fj laser without the gas additive is described in Serial No. 09/237,446, filed March 19,1999 which is incorporated herein by reference. Therefore, the scope of the invention is to be limited only by the appended claims and their legal equivalent.

We claim,
1. A method of operating a gas discharge laser having two elongated electrode, at
least one preionizer and a laser gas comprised of fluorine and a noble buffer
gas, said method comprising the steps of
A) adding to the laser gas a stabilizing additive bang chosen from a group consisting of oxygen at less than 10 ppm and a quantity at less than 100 ppm of a noble gas which is heavier than said noble buffer gas,
6) operating said laser at a repetition rate of at least 1000 pulses per second,
Wherein the adding of said stabilizing additive stabilizes laser performance without a substantial reduction in laser efficiency.
2. The method as claimed in claim 1 wherein said laser Is a Kif^ laser and said noble buffer gas is neon, and said laser gas also comprises krypton.
3. The method as claimed m claim 2 wherein said stabilizing additives is oxygen at les than 5 ppm.
4. The method as claimed in Claim 2 wherein said stabilizing additive is xenon at less than 50 ppm.
5. The method as claimed in Claim 1 wherein said laser is a ArF laser and said noble buffer gas is neon, and said laser gas also comprises argon.
6. The method as claimed in Claim 5 wherein said stabilizing additive is oxygen at less than 5 ppm.
7. The method as claimed in Claim 2 wherein said stabilizing additive is xenon at less than 50 ppm.

8. The method as claimed in Claim 7 wherein said stabilizing additive is xenon at less than 10 ppm
9. The method as claimed in Claim 8, wherein said pulse repetition rate is greater than ^00 pulses per second.
10. The method as claimed in Claim 7 wherein said laser gas defines a nominal temperature circulated past a cooling element maintained at a temperature substantially lower than said nominal temperature.
11. The method as claimed in Claim 1 wherein said laser is an F2 laser and said noble buffer gas is helium.
12. The method as claimed in Claim 11 wherein said stabilizing additive is oxygen at less than 5 ppm.
13. The method as claimed in claim 11 wherein said stability additive is xenon at less than 50 ppm.
14. The method as claimed in Claim 1 wherein said laser is operated in a thirst mode with at least 100 pulses per burst.
15. The method as claimed in Claim 14 wherein said laser defines a gas transit time, each burst defines a start time and prior to each burst the laser is pre-pulsed with at least one pulse, said at least one pulse being timed to occur not earlier than the gas transmit time prior to tile start time of each burst.
16. The method as claimed in Claim 15 wherein said at least one pulse is less than eleven pulses.

17. The method as claimed in Claim 11 wherein said at least one pulse is timed to occur about 10 ms prior to the start time of each burst.


in-pct-2002-0087-che claims-duplicate.pdf

in-pct-2002-0087-che claims.pdf

in-pct-2002-0087-che correspondence-others.pdf

in-pct-2002-0087-che correspondence-po.pdf

in-pct-2002-0087-che description(complete)-duplicate.pdf

in-pct-2002-0087-che description(complete).pdf

in-pct-2002-0087-che drawings.pdf

in-pct-2002-0087-che form-1.pdf

in-pct-2002-0087-che form-19.pdf

in-pct-2002-0087-che form-3.pdf

in-pct-2002-0087-che form-5.pdf

in-pct-2002-0087-che pct.pdf

in-pct-2002-0087-che petition.pdf

Patent Number 214470
Indian Patent Application Number IN/PCT/2002/87/CHE
PG Journal Number 13/2008
Publication Date 31-Mar-2008
Grant Date 12-Feb-2008
Date of Filing 16-Jan-2002
Name of Patentee CYMER, INC
Applicant Address 16750 Via Del Campo Court, San Diego, CA 92127-1712,
# Inventor's Name Inventor's Address
1 BESAUCELE, Herve, A. 3583 Utah Street, San Diego, CA 92104,
2 ISHIHARA, Toshihiko 7447 Salizar Street, San Diego, CA 92111,
3 HOFMANN, Thomas 4794 Arizona Street #205, San Diego, CA 92116,
PCT International Classification Number H01S 3/225
PCT International Application Number PCT/US00/18141
PCT International Filing date 2000-06-29
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/361,551 1999-07-27 U.S.A.